U.S. patent number 3,868,998 [Application Number 05/470,089] was granted by the patent office on 1975-03-04 for self-acidifying treating fluid positioning process.
This patent grant is currently assigned to Shell Oil Company. Invention is credited to George Thomas Karnes, James H. Lybarger, Ronald F. Scheuerman.
United States Patent |
3,868,998 |
Lybarger , et al. |
March 4, 1975 |
SELF-ACIDIFYING TREATING FLUID POSITIONING PROCESS
Abstract
The positioning of a treating fluid such as an acidifying or
particle-carrying fluid, in a subterranean location is improved by
injecting a viscous aqueous solution that contains a cellulose
ether, a fluoride salt and a relatively slowly reactive
acid-yielding material, and subsequently becomes a substantially
non-viscous weakly acidic liquid that is capable of dissolving
silica.
Inventors: |
Lybarger; James H. (Metairie,
LA), Scheuerman; Ronald F. (Bellaire, TX), Karnes; George
Thomas (Houston, TX) |
Assignee: |
Shell Oil Company (Houston,
TX)
|
Family
ID: |
23866225 |
Appl.
No.: |
05/470,089 |
Filed: |
May 15, 1974 |
Current U.S.
Class: |
166/278; 166/307;
166/308.1 |
Current CPC
Class: |
C09K
8/72 (20130101); E21B 43/045 (20130101); E21B
43/26 (20130101) |
Current International
Class: |
C09K
8/72 (20060101); C09K 8/60 (20060101); E21B
43/02 (20060101); E21B 43/04 (20060101); E21B
43/26 (20060101); E21B 43/25 (20060101); E21b
043/04 (); E21b 043/26 (); E21b 043/27 () |
Field of
Search: |
;166/307,308,278,280,281,282,271,300,259,250 ;252/8.55C |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Novosad; Stephen J.
Claims
What is claimed is
1. A well treating process comprising:
dissolving in an aqueous liquid at least one each of a cellulose
ether, a fluoride salt and a relatively slowly reactive
acid-yielding material, to form a pumpable viscous solution;
arranging the composition and proportions of the components of the
solution with respect to the temperature of a selected subterranean
location in which materials are to be contacted by the fluid and
the time required to pump fluid from a surface location to the
subterranean location; and
pumping fluid inclusive of the temporarily viscous solution from a
surface location to the selected subterranean location at a rate
such that the viscosity of the temporarily viscous solution remains
relatively high until the solution has substantially reached the
selected location and, in that location, the temporarily viscous
solution is or becomes a weakly acidic liquid that is capable of
dissolving siliceous material.
2. The process of claim 1 in which particles adapted to form a sand
or gravel pack or fracture propping mass of particles are suspended
in the temporarily viscous solution.
3. The process of claim 2 in which a gravel pack is formed by
pumping particles suspended in the temporarily viscous solution
into the space between a well screen or perforated liner and the
earth formations around the well.
4. The process of claim 3 in which the suspension of particles in
the temporarily viscous solution is preceeded by an acidic liquid
that contains a relatively slowly reactive pH-increasing reactant
ahead of an aqueous solution of a fluoride salt and acid-yielding
reactant in proportions adapted to form a weakly acidic solution
capable of dissolving siliceous material.
5. The process of claim 3 in which the suspension of particles in
the temporarily viscous solution is followed by an aqueous solution
containing a relatively slowly reactive pH-increasing reactant.
6. The process of claim 1 in which a fracture in a subterranean
earth formation is acidized by pumping at least one portion of the
temporarily viscous solution into the fracture.
7. The process of claim 6 in which the temporarily viscous solution
is allowed to remain substantially static in and around the
fracture for at least as long as required to convert substantially
all of the acid-yielding material in the solution to an acid.
8. The process of claim 1 in which an alternating sequence of at
least one slug of the temporarily viscous solution and at least one
slug of a relatively rapidly-reactive acid is injected into an
inhomogeneously permeable interval of subterranean earth formations
so that at least one slug of temporarily viscous solution tends to
preferentially enter a relatively permeable zone and divert a
following slug of the relatively rapidly-reactive acid into a less
permeable zone.
9. The process of claim 1 in which the cellulose ether, fluoride
salt, and acid-yielding materials are, respectively,
hydroxyethylcellulose ether, an ammonium salt of hydrofluoric acid,
and methyl formate.
10. In a process in which fluid is positioned in a selected remote
location by forming a temporarily viscous fluid and flowing it into
the selected location before the viscosity of the fluid is
significantly reduced, the improvement comprising;
dissolving in an aqueous liquid at least one each of a cellulose
ether, a fluoride salt, and a relatively slowly reacting
acid-yielding material;
arranging the solution components to provide a self-acidifying,
temporarily viscous solution in which the viscosity is
significantly reduced in response to a time-temperature exposure of
a selected severity; and
flowing the self-acidifying solution into the selected location at
a rate causing it to arrive at least substantially as soon as it
has received a time-temperature exposure of the selected
severity.
11. The process of claim 10 in which the selected location is a
subterranean region in contact with earth formations in or around
the borehole of a well.
12. The process of claim 11 in which particles adapted to form a
sand or gravel pack or fracture propping mass of particles are
suspended in the self-acidifying solution.
13. The process of claim 12 in which a gravel pack is formed by
pumping said suspension into the borehole of a well.
14. The process of claim 13 in which said suspension is pumped into
the well behind an acidic liquid that contains a relatively slowly
reactive pH-increasing reactant ahead of an aqueous solution of a
fluoride salt and acid-yielding reactant in proportions adapted to
form a weakly acidic solution capable of dissolving siliceous
material.
15. The process of claim 14 in which said suspension is pumped into
the well immediately ahead of an aqueous solution containing a
relatively slowly reactive pH-increasing reactant.
Description
RELATED PATENT APPLICATION
The present invention is related to, but distinct from, the
self-generating mud acid solution of the type described in the E.
H. Street, C. C. Templeton, E. A. Richardson patent application,
Ser. No. 411,132, filed Oct. 30, 1973, and now U.S. Pat. No.
3,828,854. The present invention involves a temporarily viscous
solution in which those self-generating mud acid solution
components are combined with a cellulose ether water thickener to
provide a solution in which both an acidification and a
viscosity-breaking occur in response to a time-temperature exposure
that is attainable in the course of flowing a treating or carrying
fluid into a selected subterranean location. The disclosures of the
prior application are incorporated herein by cross reference.
BACKGROUND OF THE INVENTION
This invention relates to a well treating process for treating or
emplacing material in a remote location such as a subterranean
region in or around a well. It is particularly useful for emplacing
a slurry of particles that form a sand or gravel pack in a well
and/or a fracture in a subterranean earth formation; for displacing
a viscous, low-fluid loss, slow-acting acidic solution along and
into the walls of such a fracture; for temporarily diverting a
fast-acting acid away from a zone that tends to act as a
"thief-zone" in a permeability-profile-improving stimulation of an
interval of inhomogeneously permeable earth formations; etc.
SUMMARY OF THE INVENTION
The invention relates to a process adapted for treating a well. A
temporarily viscous solution is formed by dissolving in an aqueous
liquid at least one each of a cellulose ether, a fluoride salt, and
a relatively slow acting acid-yielding material. The compositions
and proportions of the solution components are correlated with
respect to the temperature of a selected remote location in which
materials are to be contacted by the solution and the time required
to flow the solution into that location. The solution is flowed
into the selected location at a rate such that (a) the solution
arrives before its viscosity has significantly decreased and (b)
the materials in the selected location are contacted with a weakly
acidic solution that is capable of dissolving either siliceous s or
pH-sensitive material.
DESCRIPTION OF THE DRAWING
FIGS. 1 and 2 are schematic illustrations of portions of a well and
an adjacent reservoir.
DESCRIPTION OF THE INVENTION
The invention provides a process for emplacing a self-cleaning mass
or pack of particles in a subterranean location. Such packs are
useful in cased or uncased well boreholes and/or perforation
tunnels or openings in a well casing and a surrounding cement
sheath and earth formation, or between the walls of a fracture
within a subterranean earth formation. In forming such a pack, the
particles preferably have sizes of from about 10 to 100 U.S. mesh
sieve size. They are suspended in a temporarily viscous solution of
this invention, and the suspension is displaced into the location
to be packed before the solution becomes non-viscous. In this
procedure the particle-suspending solution becomes a
clay-dissolving weakly acidic solution that is present throughout
the mass of particles. This is uniquely advantageous. It ensures
the dissolving of any silica or other acid-soluble fine particles
(e.g., fine sand or silt or clay-sized or smaller particles) that
have been formed in or mixed with with the pack particles. Such
fine particles are commonly formed by the crushing of grains
passing through slurry injection pumps and/or formed in or
entrained in the slurry by the abrasion or erosion of grains moving
through conduits, the scraping-off or abrading of scale or metal
particles from conduits, the mixing of the fluid-suspended pack
grains with the grains of an unconsolidated reservoir formation
(e.g., along the periphery of a gravel pack), etc.
The present invention also provides an improved process for
acidizing a fracture while it is being formed and/or extended.
Slugs of the present temporarily viscous solutions can be used (by
themselves or in conjunction with other viscous acids, or the like)
as the fluid injected for forming, extending, propping or treating
a fracture. The temporarily high viscosity of the present fluids
adapts them to move through a fracture with relatively small and
relatively easily controllable amounts of fluid loss into the
fracture walls. Their subsequent conversion to a non-viscous
clay-dissolving weakly acidic solution both cleans and increases
the permeability of the fracture walls and/or mass of fracture
propping particles and makes it easy to remove subsequently
mobilized treating fluid from the fracture and the fracture
walls.
The invention also provides an improved acid-diverting procedure
for ensuring the treatment of both the less permeable and the more
permeable portions of an interval of earth formations of
heterogeneous permeability. An injection of slugs of the present
temporarily viscous fluid is alternated with slugs of a relatively
fast-acting acid so that the viscous fluid slugs tend to
preferentially enter and plug the more permeable or "thief" zones
while diverting more of the fast-acting acid to the less permeable
zones. The subsequent conversion of the present fluid to a
non-viscous fines-dissolving weakly acidic solution is highly
advantageous. It tends to remove the fines that may be formed by
the acidizing of the natural cementing materials and prevent
permeability reductions due to movements of such fines.
Cellulose ether water thickeneners suitable for use in this
invention include substantially any acid-sensitive cellulose
ethers, such as the hydroxyalkyl, carboxyalkyl, and lower alkyl
cellulose ethers, typified by hydroxyethylcellulose,
carboxymethylcellulose, methylcellulose, and the like, which are
substantially completely aqueous-liquid-soluble cellulose ethers
that form substantially completely aqueous-liquid-soluble
hydrolysis products when they are hydrolyzed in an acidic aqueous
liquid. The hydroxyethylcellulose "Natrosol," available from
Hercules Powder Company, "J-164" from Dowell, or "WG-8" from
Halliburton, are particularly suitable.
The water soluble fluoride salts used in the present process can
comprise one or more of substantially any fluoride salt that is
relatively water soluble. In various operations, such as sand or
gravel packing operations in which it is not necessary to inject
the self-acidifying liquid into relatively fine pores (such as
those in a relatively tight reservoir), portions of undissolved
fluoride salt can be suspended in the liquid system. The ammonium
salts of hydrofluoric acid, i.e., ammonium fluoride and ammonium
bifluoride, are preferred fluoride salts for use in the present
process. As known to those skilled in the art, in using ammonium
bifluoride, (NH.sub.4 HF.sub.2) it may be desirable to add enough
ammonia or ammonium hydroxide to provide substantially equimolar
amounts of ammonium and fluoride ions. However, an excess or
deficiency of ammonia or other alkaline material can be used to
increase or decrease the initial pH of the self-acidifying liquid
system where a relatively short or long delay is desirable with
respect to the production of an acidic solution. In addition, a
substantially neutral and/or relatively high-pH system can be
buffered to remain at a selected pH for a selected time and
temperature exposure. In such delay-imparting procedures it may be
desirable to increase or decrease the proportion of the
acid-forming ester of other reactant by an amount equivalent to
that used up or not needed in neutralizing the excess of or
deficiency of alkalinity.
The acid-yielding material used in the present invention can
comprise one or more of substantially any water-reactive esters
(e.g., hydrolyzable at moderate temperatures, such as about
100.degree. to 300.degree.F) of a relatively water-soluble acid
such as a carboxylic acid, phosphorus or sulphurus acid or its
like. Examples of suitable esters include the lower aliphatic
alcohol (e.g., C5) esters C.sub.1.sub.-the lower fatty acids
(C.sub.1.sub.-5) such as those ranging from methyl formate through
amyl valerate; the similar alcohol esters of hydroxyacetic acid,
oxalic acid and the like substituted and/or polybasic acids; etc.
Examples of other suitable acid-yielding materials include
hydrolyzable organic halides of the type described in the Dilgren
and Newman U.S. Pat. Nos. 3,215,199, 3,297,090 and 3,307,630, such
as the normal or isopropyl chlorides, tertiary-buytl chloride,
allyl chloride, crotyl chloride, etc.; hydrolyzable sulphonic acid
esters, such as methyl benezene sulphonate; and the like. The
water-soluble alcohol esters of water-soluble aliphatic carboxylic
acids having dissociation constants of from about 10.sup..sup.-2
(oxalic) to 10.sup..sup.-6 (butyric) are preferred.
Halogen-containing materials should not be used in situations in
which halogenated organic materials might become dissolved in or
entrained in produced crude oil that will be sent to the
refinery.
Where an initial high rate of reaction is desirable within the
temporarily viscous solution, a relatively small proportion of a
strong acid, such as hydrochloric acid can be added. This provides
the relatively fast reaction rate of a conventional mud acid, until
strong acid has been depleted.
The aqueous liquid used in forming the present self-acidifying
liquid system can comprise substantially any relatively soft,
brackish, fresh or pure water. Multivalent cations tend to
precipitate fluoride ions and increasing concentrations of
dissolved salt tend to decrease the solubility of siliceous
materials in a hydrofluoric acid-containing solution. Because of
this, a soft water that is at least as pure as fresh water is
preferred. However, chelating or sequestering agents can be used to
mitigate the effects of multivalent cations.
In general, the concentration of the cellulose ether water
thickener can be varied substantially as desired to obtain the
selected degree of temporarily high viscosity. The proportion of
dissolved cellulose material can range from about 0.1 to 4% by
weight of the solution to provide viscosity which (at normal
surface temperatures of about 80.degree.F) can range from about 100
to 51,000 centipoise, such as those which characterize relatively
viscous pumpable fluids. Where relatively large particles are to be
suspended in such fluids, the viscosities are preferably adjusted
to be relatively high, e.g., by using a relatively high proportion
of cellulosic material.
The concentrations of the fluoride salt and the acid-yielding
reactant can also be varied relatively widely. For an effective
dissolution of siliceous materials, it is desireable that the
concentration of hydrogen fluoride in the liquid become equivalent
to at least 0.1 mole per liter, and preferably, from about 1 to 2
moles/liter. The ratio of the acid-yielding material to the
fluoride salt is preferably at least about equimolar in order to
release all of the available hydrogen fluoride. Molar ratios of the
acid-yielding material to the fluoride salt of from about 1.5 to
2.5 are preferred.
As known to those skilled in the art, the severity of the
time-temperature exposure of reactive materials, such as the
present temporarily viscous aqueous solutions, are increased by
increases in either the degree of the temperature exposure for a
given time, or the duration of the exposure at a given temperature.
In a well treating operation, it is not usually feasible to make
significant changes in the temperature of the subterranean location
to be treated (or the conduit extending from it to a surface
location) although some change can sometimes be made injecting a
relatively hot or cold fluid. In addition, except in a fracturing
operation, the rate at which fluid is pumped from a surface
location to the subterranean location, is generally limited by the
rate at which fluid can be flowed into the pores of the earth
formation in response to a pressure less than the fracturing
pressure. In formulating the present temporarily viscous solutions,
the composition and proportions of the solution component are
preferably arranged to provide a viscosity reduction in response to
a time-temperature exposure that can feasibly be attained in
pumping that solution into the particular subterranean location to
be treated.
FIG. 1 illustrates a particularly suitable procedure for utilizing
the invention. It shows a well having a borehole 1 completed into a
subterranean reservoir 2. The well contains a string of casing 3
surrounded by a sheath of cement 4 and penetrated by perforations 6
that provide openings into the reservoir. A tubing string 7
connected to a screen or perforated liner 8 (with the appropriate
packing, hanging and crossover devices, etc.) for a gravel packing
operation, has been inserted within the casing.
As indicated by the arrows, fluid is pumped through the tubing
string and into the reservoir. The injected fluid preferably
comprises a series of individual portions or slugs. The slugs shown
should be preceded by a slug of fresh water or an aqueous solution
of an ammonium salt, such as ammonium chloride, where needed to
displace any reservoir water that contains a significant amount of
alkali metal or alkaline earth metal salts. Slug 9 is a pre-formed
mud acid such as a self-neutralizing mixture of hydrochloric and
hydrofluoric acids and a pH-increasing reactant. Such
self-neutralizing acid solutions are more completely described in
the E. A. Richardson, R. F. Scheuerman patent application Ser. No.
274,778 filed July 24, 1972, now U.S. pat. No. 3,826,312. The
disclosures of that application are incorporated herein by cross
reference. The disclosures of the prior application are
incorporated herein by cross-reference.
Slug 10 is a spacer fluid, such as a relatively dilute aqueous
solution of ammonium chloride. Slug 11 is a SGMA (self-generating
mud acid) of an aqueous solution of a fluoride salt and an
acid-yielding material (of the type described in the
above-identified copending patent application Ser. No. 411,132, and
now U.S. Pat. No. 3,828,854). Slug 12 is a present temporarily
viscous self-generating mud acid solution free of gravel packing
particles. Fluid 13a is a filtrate from fluid 13, which is a slurry
of gravel packing particles suspended in a temporarily viscous
self-generating mud-acid solution of the present invention. The
filtrate 13a (which comprises a temporarily viscous solution) flows
into the formation as the suspended grains are screened-out against
the formation. Fluid 13b is a supernatent liquid portion of slurry
13 (comprising a temporarily viscous solution) from which packing
particles have settled out as the slurry stands, or flow relatively
slowly, in the borehole. The slurry 13 is preferably displaced into
the desired location by an inert (or subsequently neutralizing)
displacing fluid 14, such as an aqueous solution of an ammonium
halide.
FIG. 2 shows the same portion of the well at a later stage, at
which time fluid is being flowed into the wall, or produced, from
the reservoir 2. In this stage the well contains a gravel pack 16
formed by the particles that were transported by the slurry 13. As
shown by the arrows, the produced fluid tends to enter the gravel
pack 16 and move directly into adjacent openings in the screen or
liner 8. Therefore, the production of fluid from the reservoir
leaves a substantially undisturbed column of fluid 14 and/or 13b
standing above and/or in the upper portion of the gravel pack
16.
Since fluid 14 is apt to be or be mixed with a substantially
non-viscous, but relatively weakly acidic liquid that is
subsequently formed by the self-conversion of the supernatent
temporarily viscous fluid 13b (shown in FIG. 1), the fluid 14 can
advantageously contain a pH-increasing reactant to subsequently
reduce the corrosivity of the acidic liquid.
The flow patterns of fluid injected or produced through such gravel
packs are such that the self-cleaning aspect of the present process
is uniquely advantageous. The in-situ conversion of the
particle-suspending fluid to a mud acid ensures the dissolving of
substantially all the accumulated silt-sized or clay-sized fine
particles that have become entrained within or along the
peripheries of the pack. The perforations through which fluids can
flow between the well and the reservoir are, in effect, parallel
flow paths. Therefore, if one such path is plugged, most or all of
the flow proceeds through the other. Because of this, a mud acid
that is injected after the emplacement of pack 16 is seldom
effective for dissolving fines throughout the body of the pack, or
along the interfaces between the openings through the perforations
6 and the associated perforation tunnels and the face of the
reservoir. Such a fines-dissolving action throughout all of a pack
of particles is, however, effectively accomplished by the present
process of forming an acid by a chemical conversion of the
grain-suspending fluid while it is distributed throughout the
pack.
Well Treating Temporarily Viscous Solution
A temporarily viscous solution for use in treating a well in which
the temperature in the location in which materials are to be
contacted by the fluid is about 150.degree.F is exemplified by a
solution composed of the following:
852 gallons of fresh water
65 pounds of hydroxyethylcellulose (such as "Natrosol")
205 pounds of ammonium bifluoride
28 gallons of 30% aqueous ammonium hydroxide
107 gallons of methyl formate.
The methyl formate component is preferably not added to the
solution until immediately before pumping.
Such a solution preferably contains a corrosion inhibitor. Examples
of suitable inhibitors include ammonium compounds, such as
thiourea, quaternary ammonium salts, heterocyclic nitrogen
compounds, rosin amines or the like; inorganic compounds such as
arsenic derivatives; unsaturated materials such as acetylenic
alcohols; the corrosion inhibitors available as MSA-Inhibitors from
Halliburton, E-878 inhibitors from Dowell; and the like.
Other additives such as reducing agents, chelating agents, wetting
agents and the like can be included in such a solution as long as
they do not interfere with the cellulose ether-hydrolyzing and mud
acid-generating reactions of the present invention.
Gravel Packing Well Treating Process
A particularly suitable procedure for gravel packing a well that is
completed (with an open hole, or a perforated casing or liner or
the like) into a reservoir having a temperature of about
150.degree.F is exemplified by the following. The equipment and the
sequence of fluids used are preferably those shown in FIG. 1, and
preferably follow a displacing or dissolving of any potentially
interferring minerals, such as alkaline earth metal carbonates, or
fluids--such as residual oil and/or aqueous solution of alkali
metal or alkaline earth metal salts, etc.
Fluid 9; -- 1,000 gallons self-neutralizing mud acid comprising an
aqueous solution containing 7.5% hydrochloric acid, 1.5%
hydrofluoric acid and about 2 moles/liter urea;
Fluid 10; -- 2 barrels of aqueous 3% ammonium chloride
solution;
Fluid 11; -- 2 barrels self-generating mud acid solution (in which
solution 852 gallons of fresh water are mixed with 207 pounds of
ammonium bifluoride, 28 gallons of 30% aqueous ammonia solution and
107 gallons of methyl formate);
Fluid 12; -- 3 barrels of the above-described Well Treating
Temporarily Viscous Solution containing about 3% by weight of
ammonium chloride;
Fluid 13; -- 10 barrels of a suspension of about 15 pounds per
gallon gravel packing sand, such as Ottawa 40-60 US mesh silica
sand, in the above-described Well Treating Temporarily Viscous
Solution; and
Fluid 14; -- 2 barrels of aqueous 3% ammonium chloride solution
containing about 2 moles/liter urea.
The above train of fluids is preferably displaced through the
tubing string 7 ahead of fluid 14 so that the leading edge of fluid
14 flows through the tubing string cross-over and into the annulus
between the tubing and casing above the uppermost perforation 6,
while the trailing edge remains in the tubing string 7 above the
crossover device. The so-treated well is preferably allowed to
stand for about 24 hours and then returned to production.
In using the present temporarily viscous solutions to emplace a
self-cleaning mass or pack or particles the particles which can be
used include substantially any that are relatively strong and are
inert or slowly reactive with respect to a weakly acidic solution
capable of dissolving clay or silica. Such particles preferably
have sizes of from about 10 to 100 US mesh and are preferably
relatively well-rounded grains or granules. Examples of suitable
particle materials include siliceous sand or gravel, walnut shells,
glass beads, comminuted resins, or the like. When a pack of
relatively well-rounded siliceous sand grains having sizes at least
as large as 60 mesh is emplaced in a wellbore as described above,
the silica-dissolving action of the present weakly acidic fluid
(which is self-generated throughout the pack) tends to remove any
entrained siliceous or weak acid-reactive fine materials without
causing any adverse effect, such as a significant loss of volume or
strength, within the pack.
* * * * *